CN102807782B

CN102807782B - Solid ink compositions containing hypocrystalline oligomer resin

Info

Publication number: CN102807782B
Application number: CN201210180216.1A
Authority: CN
Inventors: R·卡利尼; A·格雷德玛
Original assignee: Xerox Corp
Current assignee: Xerox Corp
Priority date: 2011-06-01
Filing date: 2012-06-01
Publication date: 2016-08-10
Anticipated expiration: 2032-06-01
Also published as: US9109124B2; DE102012208602A1; JP6016452B2; KR20120135088A; CN102807782A; US20120309896A1; JP2012251146A; DE102012208602B4; KR101773624B1; CA2778032C; CA2778032A1

Abstract

The present invention relates to a kind of solid ink compositions containing hypocrystalline oligomer resin, it is applicable to directly into the fixing ink jet printing of paper (DTP) and/or transfer.In some embodiments, described oligomer resin is poly-/oligoester and poly-/oligoamide ester compounds, and it is the non-wax material with semi-crystalline nature.

Description

Solid ink compositions containing semicrystalline oligomer resins

Technical Field

The present invention relates to a solid ink composition containing a semicrystalline oligomer resin.

Background

The solid ink compositions disclosed herein are characterized in that they are solid at room temperature and melt at an elevated temperature at which the melted ink is applied to a substrate. These solid ink compositions are useful in printing inks, and in particular, in ink jet printing inks.

Solid ink compositions for ink jet printing typically contain both a colorant and a vehicle or carrier, where the vehicle or carrier is a material that dissolves or suspends the colorant. For example, simple solid ink compositions consist of a wax as a carrier and a pigment or dye as a colorant. Many solid ink compositions primarily include crystalline polyethylene waxes and other functionalized wax components that allow for rapid phase transition from a molten liquid to a solid state and, due to their low coefficient of friction, also facilitate automated transport of printed documents through the glass platen and other subsystems of the printer. Solid ink compositions have also typically included resins as ink components. The resin makes the ink tough enough after cooling to make the ink more resistant to mechanical loads on the printed substrate, such as sticking, scratching, and creasing.

Furthermore, the use of a resin in the ink composition has the following advantages: the dye can be relatively well dissolved therein, and the pigment can be relatively easily dispersed therein. The resin also has the following advantages: their chemical composition can be easily varied to provide the physical characteristics of amorphous semi-crystalline or pure crystalline that aid in the curing of the ink.

Many conventional solid ink compositions are made from highly crystalline waxes or wax-based materials, such as polyethylene waxes, and hydrocarbon amide or ester waxes, which are very hard and resistant materials that melt quickly and crystallize (solidify) quickly upon cooling; however, these wax-based crystalline solid inks do have certain physical drawbacks. For example, solid inks comprising hard, crystalline wax-based materials are also more brittle, and therefore prints made using such inks are susceptible to damage by applied mechanical forces, such as scratching or breaking from paper creases. In addition, crystalline wax-based solid inks typically have poor adhesion to non-porous substrates, which results in poor scratch resistance and image robustness on their own. The highly non-polar nature of hydrocarbon waxes (e.g., crystalline polyethylene waxes) can also limit the solubility and miscibility of common ink compositions and special performance additives (e.g., colorants, dispersants, synergists, rheology modifiers, and antioxidants), which can lead one to having to develop conventional additives and materials for such inks.

Thus, there is a need for alternative solid ink compositions that are not based on highly crystalline polymeric waxes that can provide durable, more robust solid ink prints without the above-mentioned problems. There is also a need for alternative solid ink compositions containing more polar resins having both some degree of crystalline and amorphous character (e.g., they have semi-crystalline character) that can provide more viscoelasticity in solid inks and better compatibility with conventional ink additives and colorants. There is also an increasing need for sustainable inks comprising resins and components of biological origin that may have better biodegradability functionality than commercially available hydrocarbon wax-based inks.

Disclosure of Invention

According to embodiments described herein, novel solid ink compositions are provided that include semi-crystalline oligomeric resins, such as oligomeric amide esters, oligomeric esters, and oligomeric amide resins suitable for use in inkjet printing techniques.

In particular, embodiments of the present invention provide a solid phase change ink comprising: a semi-crystalline oligomeric resin selected from the group consisting of polyesters, oligoesters, polyesteramides and oligoesteramides; optionally a colorant; and an ink vehicle, wherein the semi-crystalline oligomeric resin is prepared from a condensation reaction of a dicarboxylic acid or anhydride or diester, a difunctional alkanol monomer, and optionally a monofunctional end-capping reactant.

In other embodiments, there is provided a solid phase change ink comprising: a semi-crystalline oligomeric resin selected from the group consisting of polyesters, oligoesters, polyesteramides and oligoesteramides; a colorant; and an ink vehicle, wherein the oligomeric resin is prepared from a condensation reaction of a dicarboxylic acid, a difunctional alkanol monomer, and optionally a monofunctional capping reactant, represented by the reaction:

wherein X is O, NH, and mixtures thereof, and in the presence of an optional end-capping agent R₃The group Z ═ O or NH in ZH. R₁、R₂And R₃Independently of each other, and may be substituted or unsubstituted, and hetero atoms may or may not be present, and further wherein R₁Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₂Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₃Is H; an alkyl group having from about 1 to about 50 carbon atoms; an aryl group having from about 6 to about 50 carbon atoms; or an alkaryl group having from about 7 to about 50 carbon atoms; and n is from about 1 to aboutNumber 10.

In other embodiments, there is provided a solid phase change ink comprising: a semi-crystalline oligomeric amide or ester resin; a colorant; and an ink vehicle, wherein the oligomeric amide ester resin has the formula

Wherein R is₁、R₂And R₃Independently of each other, and may be substituted or unsubstituted, and hetero atoms may or may not be present, and further wherein R₁Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₂Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₃Is H; an alkyl group having from about 1 to about 50 carbon atoms; an aryl group having from about 6 to about 50 carbon atoms; or an alkaryl group having from about 7 to about 50 carbon atoms; and n is a number from about 1 to about 10, and the oligoester resin has the formula:

wherein R is₁、R₂And R₃Independently of each other, and may be substituted or unsubstituted, and hetero atoms may or may not be present, and further wherein R₁Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₂Is an alkylene group having from about 1 to about 20 carbon atoms; having from about 1 to about 20 carbonsAn alkyleneoxy group of atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₃Is H; an alkyl group having from about 1 to about 50 carbon atoms; an aryl group having from about 6 to about 50 carbon atoms; or an alkaryl group having from about 7 to about 50 carbon atoms; and n is a number from about 1 to about 10.

The present invention also provides the following preferred embodiments:

1. a solid phase change ink comprising:

a semi-crystalline oligomeric resin selected from the group consisting of polyesters, oligoesters, polyesteramides and oligoesteramides;

optionally a colorant; and

an ink vehicle wherein the semi-crystalline oligomeric resin is prepared from the condensation reaction of a dicarboxylic acid or anhydride or diester, a difunctional alkanol monomer, and optionally a monofunctional end-capping reactant.

2. The solid phase change ink of embodiment 1, wherein the oligomeric resin is an oligomeric ester and has the formula:

wherein R is₁、R₂And R₃Independently of each other, and may be substituted or unsubstituted, and hetero atoms may or may not be present, and further wherein R₁Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₂Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₃Is H; an alkyl group having from about 1 to about 50 carbon atoms; aromatic hydrocarbon having about 6 to about 50 carbon atomsA group; or an alkaryl group having from about 7 to about 50 carbon atoms; and n is a number from about 1 to about 10.

3. The solid phase change ink of embodiment 1, wherein the oligomeric resin is an oligomeric amide ester and has the formula:

wherein R is₁、R₂And R₃Independently of each other, and may be substituted or unsubstituted, and hetero atoms may or may not be present, and further wherein R₁Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₂Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₃Is H; an alkyl group having from about 1 to about 50 carbon atoms; an aryl group having from about 6 to about 50 carbon atoms; or an alkaryl group having from about 7 to about 50 carbon atoms; and n is a number from about 1 to about 10.

4. The solid phase change ink of embodiment 1 wherein the oligoester resin is prepared by the polycondensation of a monomer consisting of two or more reactive functional groups, optionally a monofunctional capping reactant, selected from the group consisting of linear alkane dicarboxylic acids, branched alkane dicarboxylic acids, and (poly) cycloalkane dicarboxylic acids, ethylenically unsaturated dicarboxylic acids, arene dicarboxylic acids, alkyl arene dicarboxylic acids, aryl alkane dicarboxylic acids, hydroxy-substituted (di) carboxylic acids, alkane diols, ethylenically unsaturated diols, hydroxy-substituted diols, alkyl arene diols, aryl alkane diols, polyols; the capping reactant is selected from the group consisting of straight, branched and cyclic alkanols, ethylenically unsaturated alkanols, aryl alkanols, and mixtures thereof.

5. The solid phase change ink of embodiment 1 wherein the oligomeric amide ester resin is prepared from monomers consisting of two or more reactive functional groups, optionally a monofunctional capping reactant, selected from the group consisting of linear alkane dicarboxylic acids, branched alkane dicarboxylic acids, and (poly) cycloalkane dicarboxylic acids, ethylenically unsaturated dicarboxylic acids, arene dicarboxylic acids, alkyl arene dicarboxylic acids, aryl alkane dicarboxylic acids, primary-and secondary-aminoalkanols, hydroxy-substituted aminoalkanols, ethylenically unsaturated aminoalkanols, aminocarboxylate esters, hydroxy-substituted alkaryl amines, hydroxy-substituted aralkyl amines, polyhydroxy amines; the capping reactant is selected from the group consisting of straight, branched and cyclic alkanols, ethylenically unsaturated alkanols, aryl alkanols, and mixtures thereof.

6. The solid phase change ink of embodiment 1, wherein the ink vehicle includes a crystalline compound.

7. The solid phase change ink of embodiment 6, wherein the crystallization temperature of the ink vehicle is within ± 15 ℃ of the crystallization temperature of the oligomeric resin.

8. The solid phase change ink of embodiment 1, wherein the ink has a melting temperature of 80 ℃ or greater.

9. The solid phase change ink of embodiment 8, wherein the ink has a melting temperature of from about 80 to about 130 ℃.

10. The solid phase change ink of embodiment 1, wherein the ink has a crystallization temperature of from about 50 to about 110 ℃.

11. The solid phase change ink of embodiment 10, wherein the ink has a crystallization temperature of from about 60 to about 100 ℃.

12. The solid phase change ink of embodiment 1, wherein the ink has a viscosity greater than 1 × 10 over a temperature range from about 20 ℃ to about 60 ℃⁶cPs。

13. The solid phase change ink of embodiment 1 wherein the ink vehicle further comprises other crystalline components present in an amount of 1 to 70 percent by weight of the ink.

14. The solid phase change ink of embodiment 1 having a phase transition from a liquid (molten) state to a solid (crystalline) state at a temperature of from about 50 ℃ to about 110 ℃.

15. The solid phase change ink of embodiment 1 having an ink crystal phase transition from the liquid to the solid state at a temperature in the range of about 5 ℃ to about 15 ℃.

16. The solid phase change ink of embodiment 1, wherein the semi-crystalline oligomer resin has a molecular weight of about 500 to about 2,500 g/mol.

17. A solid phase change ink comprising:

a colorant; and

an ink vehicle, wherein the oligomeric resin is prepared from a condensation reaction of a dicarboxylic acid, a difunctional alkanol monomer, and optionally a monofunctional capping reactant, represented by the reaction:

wherein X is O, NH, and mixtures thereof, and in the presence of an optional end-capping agent R₃The group Z ═ O or NH in ZH, and R₁、R₂And R₃Independently of each other, and may be substituted or unsubstituted, and hetero atoms may or may not be present, and further wherein R₁Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₂Is an alkylene group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; arylene having about 6 to about 20 carbon atoms; or an aralkylene group having from about 7 to about 20 carbon atoms; r₃Is H; an alkyl group having from about 1 to about 50 carbon atoms; has an effect ofAryl of 6 to about 50 carbon atoms; or an alkaryl group having from about 7 to about 50 carbon atoms; and n is a number from about 1 to about 10.

18. The solid phase change ink of embodiment 17 wherein the ratio of dicarboxylic acid to difunctional alkanol monomer is from about 2:1 to about 0.5: 1.

19. A solid phase change ink comprising:

a semi-crystalline oligomeric amide or ester resin;

a colorant; and

an ink vehicle wherein the oligomeric amide ester resin has the formula:

wherein R is₁、R₂And R₃Independently of each other, and may be substituted or unsubstituted, and further wherein R₁Is a linear, branched or cyclic alkyl group having from about 1 to about 20 carbon atoms; an alkyleneoxy group having from about 1 to about 20 carbon atoms; or an aryl or heteroaryl group having from about 4 to about 10 carbon atoms; r₂Is a linear, branched or cyclic alkyl group having from about 1 to about 50 carbon atoms; an aryl group having from about 1 to about 14 carbon atoms; an alkaryl group having from about 1 to about 25 carbon atoms; or an ethylenically unsaturated alkyl group having from about 1 to about 50 carbon atoms; r₃Is H; a linear, branched, ethylenically unsaturated, or cyclic alkyl group having from about 1 to about 50 carbon atoms; an aryl or alkaryl group having from about 1 to about 25 carbon atoms; or an alkyleneoxy group having from about 1 to about 20 carbon atoms; and n is a number from about 1 to about 10, and the oligoester resin has the formula:

wherein R is₁、R₂And R₃Independently of each other, and may be substituted or unsubstituted, and further wherein R₁Is a linear, branched or cyclic alkyl group having from about 1 to about 50 carbon atoms; an ethylenically unsaturated alkyl group having from about 1 to about 40 carbon atoms; or an alkaryl group having from about 1 to about 20 carbon atoms; r₂Is a linear, branched or cyclic alkyl group having from about 1 to about 50 carbon atoms; an aryl group having from about 1 to about 14 carbon atoms; an alkaryl group having from about 1 to about 25 carbon atoms; or an ethylenically unsaturated alkyl group having from about 1 to about 50 carbon atoms; r₃Is H; a linear, branched, ethylenically unsaturated, or cyclic alkyl group having from about 1 to about 50 carbon atoms; an aryl or alkaryl group having from about 1 to about 25 carbon atoms; or an alkyleneoxy group having from about 1 to about 20 carbon atoms.

20. The solid phase change ink of embodiment 19 wherein the oligomeric polyesteramide or oligoester resin is present in an amount of about 10 to about 90 weight percent based on the total weight of the solid phase change ink.

Drawings

For a better understanding of embodiments of the present invention, reference may be made to the accompanying drawings.

FIG. 1 is a graph showing the rheology curve (complex viscosity versus temperature) of semi-crystalline oligomer resins of an embodiment of the present invention;

FIG. 2 is a graph showing ink vehicles (diurethanes and C) present for use in embodiments of the present invention₁₁Alkylated mono-oxazoline diol) of the phase change ink composition; and is

FIG. 3 is a graph showing the rheology curve (complex viscosity versus temperature) of an ink composition of an embodiment of the present invention compared to other known commercially available phase change inks.

Detailed Description

In the following description, it is to be understood that other embodiments may be utilized and structural and operational changes may be made without departing from the scope of the embodiments of the invention disclosed herein.

Solid ink technology broadens printing capabilities and consumer base across multiple markets and will promote versatility in printing applications by effectively integrating printhead technology, printing methods, and ink materials. Solid ink compositions are characterized as being solid at room temperature and melting at an elevated temperature at which the melted ink is applied to a substrate. Existing commercial solid ink printing equipment typically uses highly crystalline hydrocarbon wax-based solid inks. The wax in the ink serves both as a phase change agent, allowing the ink to melt and crystallize rapidly, and as a vehicle or carrier for the molten ink, binding the other ink components together. However, as previously discussed, while waxes provide the benefits of inks with certain jettability and image quality, wax-based inks also suffer from a variety of problems, including brittleness, which can result in poor scratch resistance and paper crease enhancement, and poor adhesion to non-porous paper and substrates, which can further exacerbate the problem of image robustness.

Embodiments of the present invention are directed to novel solid ink compositions comprising semi-crystalline oligomeric resins, such as oligomeric polyesteramides or oligoesters, and mixtures thereof, having suitable properties for direct-to-paper (DTP) and/or transfer set (transfix) ink jet printing. In embodiments, the semi-crystalline oligomeric resin includes an oligomeric amide ester compound prepared from a linear aminoalkanol and a dicarboxylic acid, which is a non-wax based material and has semi-crystalline properties. These semi-crystalline oligomeric materials exhibit a sharp crystalline phase transition from the liquid (molten) state to the solid state at temperatures from about 50 ℃ to about 100 ℃, or from about 60 ℃ to about 90 ℃, which is suitable for hot melt phase change ink jet inks. The semi-crystalline oligomer resins of the present disclosure also have amorphous characteristics, and more specifically, a glass transition (Tg) temperature range that can provide the ink composition with a certain degree of viscoelasticity, thereby reducing brittleness of the ink and enhancing rub resistance. In embodiments, the semi-crystalline oligomer compound exhibits an initial Tg temperature ranging from about-10 ℃ to about 50 ℃, or from about-5 ℃ to about 40 ℃. In addition, embodiments of the present invention provide "green" sustainable inks that include semi-crystalline oligomers made from monomers of biological origin as starting materials.

In addition, the ester and certain amide functionalities present in Poly/oligoesters and Poly/oligoesteramides are known in the literature and are said to have good biodegradation profiles, as described in Bettinger et al, Amino Alcohol-based Degradable polymers (ester amide) Elastomers, Biomaterials 29(2008) 2315-2325; montane et al, comparative degradation Data of Polyesters and Related polymers 1, 4-branched, Sebacic Acid, and α -Amino Acids, Journal of applied Polymer Science 85(2002) 1815-1824; armelin et al, Study on the degradation of Poly (Ester Amide) s degraded from the α -Amino acids Glycine, and L-Alanine contacting a Variable Amide/Ester Ratio, Polymer 42(2001) 7923-; and Qian et al, Hydrolytic degradation study of Biodegradable polymers Based on-promoter and 11-amino analytical Acid, Biomaterials 25(2004) 1975-. Thus, poly/oligoesters and poly/oligoamide esters can be used to provide "green" sustainable solid inkjet ink compositions. For example, the material may be degraded by biological action, particularly by the action of enzymes, which significantly changes the chemical structure of the material, causing it to break down into mostly water, carbon dioxide and small organic molecules.

The semi-crystalline oligomer resin also serves as a binder material that provides good adhesion to substrates (including paper and other non-porous materials), as well as binding other components of the ink composition together, such as optional crystalline phase change agents, colorants, optional viscosity modifiers, and other additives such as antioxidants to ensure good jetting performance. Embodiments of the present invention provide solid inks having a variety of beneficial properties, including a melting temperature of 80 ℃ or lessHigher, such as from about 80 ℃ to about 130 ℃, or from about 90 ℃ to about 120 ℃, ink crystallization temperature from about 50 ℃ to about 100 ℃, or from about 60 ℃ to about 90 ℃, and large viscosity changes (e.g., viscosity changes greater than 10 during ink crystallization (curing) phase transitions in the temperature range of only from about 5 ℃ to about 20 ℃, or from about 7 ℃ to about 15 ℃, or from about 8 ℃ to about 13 ℃.)⁵cPs or from about 10cPs to about 10⁶cPs). Thus, the oligomeric resins of the present invention, which may be oligomeric ester or oligomeric amido ester compounds or mixtures thereof and provide the solid ink with a semicrystalline component, can provide the jettable solid ink with a desired rheology profile and make it desirable for ink jet printing.

A general synthetic scheme for preparing semi-crystalline oligomeric resins, such as oligomeric ester and oligomeric amidoester compounds, according to embodiments of the present invention is as follows:

as indicated above, the dicarboxylic acid is reacted with a difunctional alkanol monomer, such as an alkanediol (when X ═ O), or an aminoalkanol (when X ═ NH), and mixtures thereof, in the presence of an optional end-capping agent consisting of R₃-ZH represents, which may be a monoalcohol R when Z ═ O₃-OH, when Z ═ NH can be monoamine R₃-NH₂。

In embodiments, the semi-crystalline oligomer resin may be made from a variety of alkane dicarboxylic acids, which may be linear, branched, or cyclic, and may also be aromatic or heteroaromatic, where the aryl group may contain additional alkyl substituents up to 6 carbon atoms, or other functional group substituents such as halogens F, Cl, Br, I, OH, OCH₃、OCH₂CH₃Amino, COOH, COOR (wherein R is an alkyl group having up to 10 carbon atoms), SO₃H, and the like. Exemplary dicarboxylic acids include 1, 12-dodecanedioic acid, 1, 18-octadecanedioic acid, azelaic acid (1, 9-azelaic acid), sebacic acid(1, 8-octanedioic acid), adipic acid (1, 6-adipic acid), succinic acid (1, 4-succinic acid), 1, 4-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, C-36 dimer acid, terephthalic acid, isophthalic acid, phthalic acid, anhydrides such as phthalic anhydride and succinic anhydride, and many other compounds.

In embodiments, the semi-crystalline oligomer resin may be prepared from any suitable difunctional alkanol monomer, such as an alkanediol or an aminoalkanol, where the alkyl portion of the monomer may be linear, branched, or cyclic. The alkanol moiety may also contain aromatic and heteroaromatic groups of up to 6 carbon atoms, which may be further substituted by groups such as halogen F, Cl, Br, I, OH, OCH₃、OCH₂CH₃Amino, COOH, COOR (wherein R is an alkyl group having up to 10 carbon atoms), SO₃H, and the like.

In embodiments, the ratio of dicarboxylic acid to difunctional alkanol monomer is from about 2:1 to about 0.5: 1.

In an embodiment of the invention, the semi-crystalline oligomeric resin is an oligomeric amide ester compound having the structure:

wherein R is₁、R₂And R₃Independently of one another and may be substituted or unsubstituted, and further wherein R₁Is an alkyl group having from about 1 to about 20 carbon atoms, or from about 1 to about 10 carbon atoms, such as methyl, ethyl, butyl, and the like; alkyleneoxy groups having from about 1 to about 20 carbon atoms, or from about 1 to about 10 carbon atoms, such as methyleneoxy, ethyleneoxy, and the like; or an aryl or heteroaryl group having from about 4 to about 10 carbon atoms, such as phenyl, pyridyl, naphthyl, and the like; r₂Is an alkyl or aryl group as defined above; r₃Is an alkyl or aryl group as defined above; n is a number from about 1 to about 10. In other embodiments, R₁Is alkyl, alkyleneoxy or aryl, R₂Is alkyl or aryl, and R₃Is an alkyl or aryl group. Specific examples of oligomeric amidoester resins of the present disclosure are set forth in table 1 below.

TABLE 1

Example 7 was carried out under reaction conditions different from those of example 1.

The plot is a plot of complex viscosity versus temperature as measured by a Rheometrics RFS3 instrument at a constant frequency of 1Hz with a parallel plate geometry tool at 200% applied strain.

In an embodiment of the present invention, the semi-crystalline oligomer resin may also be an oligoester having the structure:

wherein R is₁、R₂And R₃Independently of each other and may be substituted or unsubstituted, and further wherein R₁Is a linear, branched or cyclic alkyl group having from about 1 to about 50 carbon atoms; an ethylenically unsaturated alkyl group having from about 1 to about 40 carbon atoms; or is an alkaryl group having from about 1 to about 20 carbon atoms; r₂Is a linear, branched or cyclic alkyl group having from about 1 to about 50 carbon atoms; an aryl group having from about 1 to about 14 carbon atoms; an alkaryl group having from about 1 to about 25 carbon atoms; or an ethylenically unsaturated alkyl group having from about 1 to about 50 carbon atoms; r₃Is H; a linear, branched, ethylenically unsaturated, or cyclic alkyl group having from about 1 to about 50 carbon atoms; an aryl or alkaryl group having from about 1 to about 25 carbon atoms; or from about 1 to about 20 carbonsAn alkyleneoxy group of an atom.

In embodiments of the present invention, non-waxy and biodegradable semi-crystalline oligomeric resins, such as oligomeric amidoester compounds prepared from aminoalkanols, as illustrated by the general synthetic schemes shown above, are provided, as well as novel phase change ink compositions containing these resins. The ink compositions of the present disclosure may be used in direct-to-paper (DTP) or transfer set inkjet printing processes. Specific examples of the oligoester resins of the present disclosure are set forth in table 2 below.

TABLE 2

In embodiments, the oligomeric amide ester is semi-crystalline and exhibits a sharp phase transition through a narrow temperature range of about 10-15 ℃ when crystallized from the molten state. In order to have a sufficiently low viscosity at the desired jetting temperature that enables the ink to be jettable, the resulting oligomeric resin has a low molecular weight (e.g., in the range of about 500 to about 2,500g/mol, or about 600 to about 2000 g/mol), and can also be used as a binder resin for the ink (as an ink vehicle, that is, more than 50% by weight of the ink content) in combination with another crystalline low molecular weight phase change agent or viscosity modifying component. Since this resin is also semi-crystalline, its inherent phase change properties provide for the crystallization enhancement of the ink.

By combining the oligomeric amide ester with the viscosity modifier vehicle component, a phase change (solid) ink formulation has been developed that has a relatively low melt viscosity at jetting temperatures of from about 100 ℃ to about 150 ℃, or from about 110 ℃ to about 140 ℃. In embodiments, the viscosity modifier vehicle component is a crystalline compound, which may be selected from alkane carbamates, alkane dicarbamates, alkylamides such as stearamide, erucamide, behenamide, stearoyl stearamide, alkyl esters of monosaccharides (e.g., sorbitol, mannitol), and derivatives such as tartaric acid, malic acid, and the like, and alkyl mono-oxazoline diols, which are disclosed in U.S. patent application 13/095,221, filed 2011, 4/27, the disclosure of which is incorporated herein, and mixtures thereof. Specific embodiments of such crystalline phase change agents and their properties are set forth in Table 3 below.

TABLE 3

Compound 1 of table 3 is a crystalline dicarbamate compound disclosed in U.S. patent 7,560,587, which is incorporated herein by reference in its entirety. Compound 2 of table 3 is a C-11 alkylated mono-oxazoline diol, another crystalline compound disclosed in U.S. patent application 13/095,221. Compound 3 is a crystalline diester, which is disclosed in U.S. patent application 13/196,227, Goredema et al, filed 2011, 8/2 (attorney docket No. 20101649-US-NP).

FIG. 2 provides a complex viscosity-temperature curve of the phase change ink components of Table 3, showing a crystalline phase transition: (i) at about 90 ℃ to 92 ℃ for dicarbamate (compound 1 of table 3), and (ii) at 88 ℃ for C-11 alkylated mono-oxazoline diol (compound 2 of table 3). These compounds are compatible with and easily blended with the oligoamide ester resin of example 1, and have a crystalline transition within the narrow range of the semi-crystalline transition of the oligoamide ester binder resin of example 1, and are suitable as supplemental vehicle or carrier components of the disclosed ink compositions.

In embodiments, the ink vehicle also contains other crystalline components. These components may be present in the ink vehicle in an amount of 1 to 70% by weight of the ink. In embodiments, when the vehicle component is a crystalline compound (which is optional and may be preferred in certain compositions), then the component has a crystallization temperature within ± 10 ℃ to ± 15 ℃ of the crystallization temperature of the selected semi-crystalline oligomer resin. The optional crystalline ink vehicle component is selected to have a lower viscosity at the desired jetting temperature than the semi-crystalline oligomer resin at that jetting temperature. More preferably, the viscosity of the optional crystalline ink vehicle component should not exceed the viscosity of the final inkjet ink composition, thereby ensuring a suitable viscosity to achieve good jetting performance. The relative amounts of the semi-crystalline oligomeric binder resin and the optional crystalline ink component, the latter having a low viscosity, should be such that the final viscosity of the ink vehicle is in the range of from about 9 to about 14cPs, or from about 9.5cPs to about 13cPs, or from about 10cPs to about 12cPs, and the ink crystallization temperature is in the range of from about 55 ℃ to about 105 ℃, or from about 60 ℃ to about 100 ℃, or from about 65 ℃ to about 95 ℃. In embodiments, to achieve these ink properties, the proportion in the ink composition should be from about 10 to about 90 wt%, or from about 10 to about 70 wt%, or from about 15 to about 60 wt% of the semi-crystalline oligomeric binder resin, with from about 10 to about 70 wt%, or from about 20 to about 60 wt% of the optional crystalline binder component. Furthermore, in embodiments of the present invention, the ink consistency should have an overall homogeneous phase, no significant component density gradient, or visible phase-separated micro-crystalline domains.

The colorant selected for use in the ink composition in embodiments of the present invention may be a dye or a pigment, and should have good compatibility with the ink components. While the amount of colorant used in the ink depends on the spectral intensity of the colorant selected, a typical range of dyes or pigments can be from about 1 to about 5 weight percent of the ink composition. Additional additives in the ink, such as antioxidants, are used in such formulations in conventional amounts — typically less than about 1% by weight of the ink composition is added.

Table 4 below provides several ink formulations of embodiments of the present invention

TABLE 4

As an example, ink example 1 is a phase change solid ink comprising two specific oligomeric amidoester resins of the present embodiment, example 1 resin and example 2 resin, in amounts of 16.0 and 12.3 weight percent of the ink composition. The lower viscosity binder component of choice is the crystalline phase change compound undecyl-substituted mono-oxazoline diol, which is disclosed in U.S. patent application 13/095,221, which is hereby incorporated by reference in its entirety. The mono-oxazoline compound is added in an amount of about 64 percent by weight of the ink. Viscosity modifier, S-180 (also known as Kemamide or stearyl stearamide), was added as a rheology modifier at about 4.5 weight percent to provide a suitable spray viscosity at 130 ℃. The commercially available colorant selected was Orasol from Ciba Geigy^TMBlue GN (copper phthalocyanine dye) was added in an amount of 3% by weight of the ink. Finally, a commercial antioxidant, Naugard, was added in a small amount of 0.2% by weight of the ink^TM445. The ink components were added together in the order described above and melt mixed at 130 ℃ for at least 1 hour, then poured into a mold and cooled to form a solid ink. The final ink had a viscosity of 12.5cPs at 130 ℃, an initial crystallization of 82 ℃ (as determined by frequency-1 Hz rheology) and a narrow liquid to solid phase transition spanning from about 85 ℃ to about 75 ℃ (about 10 ℃ range).

FIG. 3 shows the complex viscosity-temperature curve (complex viscosity versus temperature, constant frequency 1Hz) for ink example 1 with a sharp phase change transition and compares it to known commercially available solid inks, including those available from Xerox Corp. Fig. 3 demonstrates that inks comprising semi-crystalline oligomeric resins according to embodiments of the present invention have satisfactory thermal and rheological properties intermediate between two commercially available inks, designated commercial solid ink 1 (from Xerox Corp.) and commercial solid ink 2 (not from Xerox Corp.), but somewhat similar to Xerox inks.

The inks of embodiments may also include conventional additives to take advantage of the known functionality of such conventional additives. Such additives may include, for example, at least one isocyanate-derived functional material, antioxidants, defoamers, slip and leveling agents, clarifiers, viscosity modifiers, binders, plasticizers, dispersants, synergists, and the like.

The ink vehicle or carrier may also include at least one isocyanate-derived material. The isocyanate-derived material may be a urethane compound prepared by reacting two equivalents of an alcohol, such as hydroabietyl alcohol, with one or more equivalents of an isocyanate or diisocyanate (isophorone diisocyanate), as disclosed, for example, in example 1 of U.S. Pat. No. 5,782,966, the disclosure of which is hereby incorporated by reference in its entirety. Another example of an isocyanate-derived material is the urethane compound of example 6, which is an example of a class of crystalline diurethane compounds, disclosed in U.S. patent 7,560,587, which is incorporated herein by reference in its entirety. Other suitable isocyanate-derived materials include the reaction product of three equivalents of stearyl isocyanate with a trifunctional alcohol such as glycerol, i.e., a urethane compound, which is prepared according to example 4 of U.S. Pat. No. 6,309,453, the disclosure of which is hereby incorporated by reference in its entirety. The isocyanate-derived material is present in the ink vehicle in an amount of at least about 2% by weight of the ink composition, for example from about 2 to about 70% by weight of the ink composition, from about 5 to about 65% by weight of the ink composition, from about 8 to about 60% by weight of the ink composition, and from about 10 to about 60% by weight of the ink composition. The ink may optionally contain an antioxidant to protect the image from air or photo-oxidation, and may also protect the ink composition from oxidation when present in the ink container in the molten state. Examples of suitable antioxidants include (1) N, N '-hexamethylenebis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamamide) (IRGANOX 1098, available from Ciba Inc.), (2)2, 2-bis (4- (2- (3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)) ethoxyphenyl) propane (TOPANOL-205, available from ICI America Corporation), (3) tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate (CYANOX 1790,41,322-4, LTDP, Aldrich D12,840-6), (4)2, 2' -ethylidene bis (4, 6-di-tert-butylphenyl) fluorophosphonite (ETHANOX-398, available from Ethyl Corporation), (5) Tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenylbisphosphonite (ALDRICH46,852-5; hardness number 90), (6) pentaerythrityl tetrastearate (TCI America # PO739), (7) tributylammonium hypophosphite (Aldrich 42,009-3), (8)2, 6-di-tert-butyl-4-methoxyphenol (Aldrich25,106-2), (9)2, 4-di-tert-butyl-6- (4-methoxybenzyl) phenol (Aldrich 23,008-1), (10) 4-bromo-2, 6-dimethylphenol (Aldrich34,951-8), (11) 4-bromo-3, 5-dimethylphenol (Aldrich B6,420-2), (12) 4-bromo-2-nitrophenol (Aldrich 30,987-7), (13)4- (diethylaminomethyl) -2, 5-dimethylphenol (Aldrich 14,668-4), (14) 3-dimethylaminophenol (Aldrich ID14,400-2), (15) 2-amino-4-tert-amylphenol (Aldrich 41,258-9), (16)2, 6-bis (hydroxymethyl) -p-cresol (Aldrich22,752-8), (17)2, 2' -methylenediphenol (Aldrich B4,680-8), (18)5- (diethylamino) -2-nitrosophenol (Aldrich 26,951-4), (19)2, 6-dichloro-4-fluorophenol (Aldrich28,435-1), (20)2, 6-dibromofluorophenol (Aldrich 26,003-7), (21) alpha-trifluoro-o-cresol-1 (Aldrich 21,979-7), (22) 2-bromo-4-fluorophenol (Aldrich 30,246-5), (23) 4-fluorophenol (Aldrich F1,320-7), (24) 4-chlorophenyl-2-chloro-1, 1, 2-tris-fluoroethylsulfone (Aldrich13,823-1), (25)3, 4-difluorophenylacetic acid (Aldrich 29,043-2), (26) 3-fluorophenylacetic acid (Aldrich 24,804-5), (27)3, 5-difluorophenylacetic acid (Aldrich 29,044-0), (28) 2-fluorophenylacetic acid (Aldrich 20,894-9), (29)2, 5-bis (trifluoromethyl) benzoic acid (Aldrich32,527-9), (30) ethyl 2- (4- (4- (trifluoromethyl) phenoxy) propionate (Aldrich25,074-0), (31) Tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenyldiphosphonite (Aldrich46,852-5), (32) 4-tert-amylphenol (Aldrich 15,384-2), (33)3- (2H-benzotriazol-2-yl) -4-hydroxyphenylethanol (Aldrich 43,071-4), NAUGARD 76, NAUGARD 445, NAUGARD 512, and NAUGARD 524 (manufactured by Chemtura Corporation), and the like, and mixtures thereof. The antioxidant, when present, can be present in the ink in any desired or effective amount, for example, from about 0.25% to about 10% by weight of the ink, or from about 0.5% to about 5% by weight of the ink.

The ink may also contain an optional thickener such as a commercially available derivative of rosin acid derived from rosin or tall oil rosin. Representative examples include, but are not limited to, glycerol esters of hydrogenated rosin acids such as FORAL 85, glycerol esters of hydrogenated rosin acids (available from Eastman), FORAL 105, pentaerythritol esters of hydrogenated rosin acids (available from Eastman), CELLOLYN 21, hydrogenated rosin alcohol esters of phthalic acid (available from Eastman), ARAKAWA KE-311 and KE-100 resins, triglycerides of hydrogenated rosin acids (available from Arakawa Chemical Industries, Ltd.), synthetic polyterpene resins such as NEVTAC 2300, NEVTAC 100 and NEVTACO 80 (available from Neville Chemical Company), WINGTACK 86, modified synthetic polyterpene resins (available from Sartomer), and the like. The thickener may be present in the ink in any effective amount, such as from about 0.01% by weight of the ink to about 30% by weight of the ink, from about 0.1% by weight of the ink to about 25% by weight of the ink, from about 1% by weight of the ink to about 20% by weight of the ink.

Plasticizers such as UNIPLEX 250 (available from Unitex), phthalate plasticizers available from Ferro under the trade name SANTICIZER, e.g., dioctyl phthalate, di (undecyl) phthalate, alkyl benzyl phthalate (SANTICIZER 278), triphenyl phosphate (available from Ferro), KP-140, tributoxyethyl phosphate (available from great lakes Chemical Corporation), MORFLEX 150, dicyclohexyl phthalate (available from MORFLEX Chemical Company Inc.), trioctyl trimellitate (available from sigmaldrich Co.), and the like. The plasticizer may be present in an amount of from about 0.01 to about 30%, from about 0.1 to about 25%, from about 1 to about 20%, by weight of the ink.

When present, the optional additives can be present in the ink individually or in combination in any desired or effective amount, for example from about 0.1 to about 15% or from about 0.5 to about 12% by weight of the ink. In embodiments, the phase change ink compositions described herein also include a colorant. Any desired or effective colorant can be used in the phase change ink composition, including dyes, pigments, mixtures thereof, and the like, so long as the colorant is soluble or dispersible in the ink vehicle. Any dye or pigment can be selected so long as it is dispersible or soluble in the ink vehicle and is compatible with the other ink components. The phase change ink vehicle compositions may be used in combination with conventional colorant materials, such as Color Index (c.i.) solvent dyes, disperse dyes, modified acid dyes and direct dyes, basic dyes, sulfur dyes, vat dyes, and the like. Examples of suitable Dyes include Neozapon Red 492(BASF), Orasol Red G (Ciba), Direct Brilliant Pink B (organic Giant Dyes), Direct Red 3BL (Classic Dyes), Superanol Brilliant Red 3BW (Bayer AG), Lemon Yellow 6G (United chemical), Light Fast Yellow 3G (Shaanxi), Aizen luminescent Yellow C-GNH H Hodogaya chemical), Beschrome Yellow B (Classic Dyes), Carbosol Yellow 4 (Clariant), Cibanon Yellow 2 (Ciba), Orasol CN (Black SN), Blacking Blue (Black 61BG), Blazanyl Blue (Black 614) (Classif), Blue Yellow (Blue Yellow) Blue (Blue Yellow) 750, Blue Yellow (Blue Yellow) Blue Yellow (Blue Yellow) Yellow 670, Blue Yellow (Blue Yellow) Blue Yellow 3G (Yellow), Blue Yellow (Yellow) Blue Yellow 750 (Yellow) Blue Yellow (Blue Yellow) Blue Yellow S) (Blue Yellow 670), Blue Yellow (Blue Yellow S) (Blue Yellow 750) Sudan Yellow 146(C.I.12700) (BASF), Sudan Red 462(C.I.26050) (BASF), C.I.disperse Yellow 238, Neptune Red Base NB543(BASF, C.I.solvent Red 49), Neopen Blue FF-4012 from BASF, Lamponol Black BR (C.I.solvent Black 35) from ICI, Morton Morplas magenta 36(C.I.solvent Red 172), metal phthalocyanine dyes such as those disclosed in U.S. Pat. No. 6,221,137, the disclosure of which is hereby incorporated by reference in its entirety, and the like. Other suitable dyes include those disclosed in U.S. patent application publication 2010/0086683 and U.S. patents 7,732,581, 7,381,831, 6,713,614, 6,646,111, 6,590,082, 6,472,523, 6,713,614, 6,958,406, 6,998,493, 7,211,131, and 7,294,730, the disclosures of each of which are hereby incorporated by reference in their entirety. Polymeric dyes, such as those disclosed in U.S. Pat. No. 5,621,022 and U.S. Pat. No. 5,231,135, the disclosures of each of which are herein incorporated by reference in their entirety, and Milliken Ink Yellow 869, Milliken Ink Blue 92, Milliken Ink Red 357, Milliken Ink Yellow 1800, Milliken Ink Black 8915-67, unicount Reactant Orange X-38, unicut Reactant Blue X-17, Solvent Yellow 162, Acid Red 52, Solvent Blue44, and unicut Reactant Violet X-80, available from Milliken & Company, may also be used. In embodiments, solvent dyes are used. Pigments may also be suitable colorants for phase change inks.

In embodiments, solvent dyes are used. Examples of suitable solvent dyes include Neozapon Red 492(BASF), Orasol Red G (Ciba), Direct Brilliant Pink B (GlobalColors), Aizen Spilon Red C-BH (Hodogaya chemical), Kayanol Red 3BL (Nippon Kayaku), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (Hodogaya chemical), Cartasol Brilliant Yellow 4GF (Clariant), Pergasol Yellow CGP (Ciba), Orasol Black RLP (Ciba), Savinyl BlackRLS (Clariant), Morfast Conc.A (Rohm and Haas), Orasol Ba (Ciba), Savinyl RLS (Black RLS (Clariant), Moraxel Blue Conc.A (Rohm and Haas), Blue Yellow (BAS), Blue Yellow S (BAS S) (BAS), Blue S.S.S.S.S.S.S.S.S.S.S. Bluex), Blue Yellow S.S.S. Pat. 5 (BASF.S. Bluex, BAS., Bluex et al., BAS., Bluex (BAS., Bluex, BAS., Bluex et al., Bluex (BAS., Bluex, BAS. S. 5. S. Bluewash S. 3, BAS., Bluex, BAS. 3, and Bluewash S. 3, BAS, BAS. 3, BAS, and B.

Pigments may also be suitable colorants for phase change inks. Examples of suitable pigments include PALIOGEN VIOLET 5100 (available from BASF), PALIOGEN VIOLET 5890 (available from BASF), HELIOGEN Green L8730 (available from BASF), LITHOL SCRATD 3700 (available from BASE), SUNFAST Blue 15:4 (available from Sun Chemical), HOSTAPERM Blue B2G-D (available from Clariant), HOSTAPERM Blue B4G (available from Clariant), Permanent Red P-F7RK, HoSTAPERM VIOLET BL (available from Clariant), LITHOOL SCRATRE 40 (available from BASF), Bon Red C (available from domino Cold Company), ACORPIPE RE (available from Ciba), PALIOGEN Red 1K (available from BASF 387F), SUN Red C (available from SUOGN 15: 33), SUNFET 33 (available from Sun Chemical)40 (available from BASF), SUNFASTCarbazole Violet 23 (available from Sun Chemical), LITHOL Fast Scarlet L4300 (available from BASE), SUNBRITE Yellow 17 (available from Sun Chemical), HELIOGEN Blue L6900, L7020 (available from BASF), SUNBRITE Yellow 74 (available from Sun Chemical), SPECTRA PAC C Orange 16 (available from Sun Chemical), HELIOGEN Blue K6902₇K6910 (available from BASF), SUNFASTMagenta 122 (available from Sun Chemical), HELIOGEN Blue D6840, D7080 (available from BASF), Sudan Blue OS (available from BASE), NEOPEN Blue FF4012 (available from BASF), PV Fast Blue B2GO1 (available from Clariant), IRGALITE Blue BCA (available from Ciba), PALOGEN Blue 6470 (available from BASE), Sudan Orange G (available from Aldrich), Sudan Orange 220 (available from OrBASF), PALOGEN Orange 3040(BASF), PALOGEN Yellow 152, PALOGEN 1560 (available from BASF), LITHOOL Fast Yellow 0991K (available from BASE), PALOL Yellow1840 (available from BASF), SUNFASM Yellow 1355 (available from BASF), SUANT Yellow VP 1355 (available from BASF), BAS Yellow 1355 (available from BASF), BASYEL Yellow 1355 (available from BASF), BASYyellow 1355 (available from BASF), BASE Yellow 1355 (available from inorganic Yellow) and SANTO Yellow 1355 (available from BASF), BASE Yellow, HOSTAPERM Pink E02 (available from Clariant), Hansa Brilliant Yellow 5GX03 (available from Clariant), Permanent Yellow GRL02 (available from Clariant), Permanent Rubine L6B 05 (available from Clariant), FANALPink D4830 (available from BASF), CINQUASIA Magenta (available from DU), PALIOGEN Black L0084 (available from BASF), Pigment Black K801 (available from BASF), and carbon blacks such as REGAL 330^TM(available from Cabot), Nipex 150 (available from Degussa), Carbon Black 5250 and Carbon Black 5750 (available from Columbia chemical), and the like, and mixtures thereof.

Likewise suitable colorants are disclosed in U.S. patent 6,472,523, U.S. patent 6,726,755, U.S. patent 6,476,219, U.S. patent 6,576,747, U.S. patent 6,713,614, U.S. patent 6,663,703, U.S. patent 6,755,902, U.S. patent 6,590,082, U.S. patent 6,696,552, U.S. patent 6,576,748, U.S. patent 6,646,111, U.S. patent 6,673,139, U.S. patent 6,958,406, U.S. patent 6,821,327, U.S. patent 7,053,227, U.S. patent 7,381,831 and U.S. patent 7,427,323, U.S. patent 7,905,954, U.S. patent 7,503,973, U.S. patent 7,465,348, the disclosures of each of which are. The ink may also contain one or more dispersants and/or one or more surfactants to achieve its known properties, such as moisture control of the pigment in the ink composition. Examples of suitable additives that may be used in embodiments include, but are not limited to: BYK-UV 3500, BYK-UV 3510(BYK-Chemie), Dow Corning 18, 27, 57, 67 additives, ZONYLFSO 100(DuPont), MODAFLOW 2100(Solutia), Foam Blast 20F, 30, 550(Lubrizol), EFKA-1101, -4046, -4047, -2025, -2035, -2040, -2021, -3600, -3232, SOLSPERSE 13000, 13240, 17000, 19200, 20000, 34750, 36000, 39000, 41000, 54000, a single synergist or combination may optionally be used with synergists including SOLSPERSE 5000, 12000, 22000(Lubrizol), DISPERBYK-108, -163, -167, 182(BYK-Chemie), K-RSE 132, XD-A503, XD-A505(King Industries).

In embodiments, solvent dyes are used. One example of solvent dyes suitable for use herein can include alcohol soluble dyes because of their compatibility with the ink vehicles disclosed herein. Examples of suitable alcohol soluble dyes include Neozapon Red 492(BASF), Orasol Red G (Ciba), Direct Brilliant Pink B (Global Colors), Aizen Spilon Red C-BH (Hodogaya chemical), Kayanol Red 3BL (Nippon Kayaku), Spirit FastYellow 3G, Aizen Spilon Yellow C-GNH (Hodogaya chemical), Cartasol Brilliant Yellow 4GF (Clariant), Pergasol Yellow CGP (Ciba), Australine Black RLP (Ciba), Savinyl Black RLS (Clariant), Morfast Black Conc.A (Rohm and Haas), Orasol Fastsa (Ciba), Blasyl Blue RLS (Sanvial RLs), Blasol Blue Yellow G (BAS S61462), Blue Yellow 310G (BASF.103), Blue Yellow 310 ℃, Blue Yellow 310G (BASF # 85), Blue Yellow S (BASF # 85), Blue Yellow SO 3G, Blue Yellow NO. 5, Blue AS), Blue Yellow NO. 5 (BASF, BASF # S.103), Blue Yellow S. 5, BASF, Blue Yellow NO. 3G (BASF, Blue Yellow S. 3, Blue Yellow S (BASF, Blue Yellow S. 3, Blue S. 5, Blue Yellow NO. 3B, Blue S. 3B, Blue S (BASF, Blue S. 3, Blue S, BASF, BAS.

The colorant can be present in the phase change ink in any desired or effective amount to achieve a desired color or hue, for example, from about 0.5% to about 20% or from about 1% to about 15% or from about 2% to about 10% by weight of the ink composition. In embodiments, the melting point of the ink vehicle of the phase change ink may be from about 50 ℃ to about 140 ℃, such as from about 60 ℃ to about 120 ℃, from about 65 ℃ to about 110 ℃, as determined by Differential Scanning Calorimetry (DSC), or as visually observed and measured, for example, on a microscope hot stage. Further, the phase change ink has an jetting viscosity of about 9 to about 14cPs, for example about 10 to about 13cPs, about 10.5 to about 12cPs at an ink melting point of about 100 to about 140 ℃.

The ink composition may be prepared by any desired or suitable method. For example, the individual components of the ink vehicle can be mixed together, after which the mixture is heated to at least its melting point, e.g., about 60 ℃ to about 150 ℃,80 ℃ to about 120 ℃, and 85 ℃ to about 110 ℃. The colorant may be added before the ink ingredients are heated or after the ink ingredients are heated. When pigments are selected as the colorant, the molten mixture may be milled in an attritor or ball mill apparatus to achieve dispersion of the pigment in the ink vehicle. The heated mixture is then stirred for a period of about 5 seconds to about 10 minutes or more to obtain a sufficiently uniform, consistent melt, after which the ink is cooled to ambient temperature (typically about 20 ℃ to about 25 ℃). The ink is solid at ambient temperature. In one particular embodiment, during formation, the ink in the molten state is poured into a mold and then allowed to cool and solidify to form an ink stick. Suitable ink preparation techniques are disclosed in U.S. patent 7,186,762, the disclosure of which is hereby incorporated by reference in its entirety.

The inks can be used in an apparatus for an ink jet printing process directly to paper or indirectly to an intermediate transfer member (e.g. offset printing). Another embodiment disclosed herein is directed to a method comprising incorporating an ink as disclosed herein into an ink jet printing apparatus, melting the ink, and then causing droplets of the melted ink to be ejected in an imagewise pattern onto a recording substrate. A direct printing process is also disclosed, for example, in U.S. patent No. 5,195,430, the disclosure of which is hereby incorporated by reference in its entirety. Another embodiment disclosed herein is directed to a process comprising incorporating an ink as disclosed herein into an ink jet printing apparatus, melting the ink, causing droplets of the melted ink to be ejected in an imagewise pattern onto an intermediate transfer member, and then transferring the ink in the imagewise pattern from the intermediate transfer member to a final recording substrate. In one embodiment, the intermediate transfer member is heated to a temperature above the final recording sheet and below the temperature of the molten ink in the printing apparatus. In another embodiment, both the intermediate transfer member and the final recording sheet are heated; in this embodiment, both the intermediate transfer member and the final recording sheet are heated to a temperature below the temperature of the molten ink in the printing apparatus; in this embodiment, the relative temperatures of the intermediate transfer member and the final recording sheet may be: (1) heating the intermediate transfer member to a temperature above the final recording substrate and below the molten ink in the printing apparatus; (2) the final recording substrate is heated to a temperature above the intermediate transfer member and below the molten ink in the printing apparatus; or (3) the intermediate transfer member and the final recording sheet are heated to almost the same temperature. A method of offset or indirect printing is also disclosed, for example, in U.S. Pat. No. 5,389,958, the disclosure of which is hereby incorporated by reference in its entirety. In one embodiment, the printing apparatus uses a piezoelectric printing process in which droplets of ink are caused to be ejected in an imagewise pattern by oscillation of a piezoelectric vibrating element. The inks disclosed herein can also be used in other hot melt printing processes, such as hot melt ultrasonic ink jet printing, hot melt sublimation ink jet printing, hot melt continuous flow or deflection ink jet printing, and the like. The phase change inks disclosed herein can also be used in printing processes other than hot melt ink jet printing processes, such as hot melt lithographic, flexographic, and related offset ink printing processes.

Any suitable substrate or recording sheet may be used, including plain paper (paper) such as XEROX 4200 paper, XEROX image series paper, Courtland 4024DP paper, grid notebook paper, security paper, silica coated paper such as Sharp Company silica coated paper, JuJo paper, HAMMERMILL LASERPRINT paper, coated and heavy paper stock such as XEROX Digital Color Elite Gloss paper, transparency material, fabric, textile products, plastics, flexible polymeric films, inorganic substrates such as metal or silicon wafers, wood, and the like. The inks described herein are further illustrated in the following examples. All parts and percentages are by weight unless otherwise indicated.

It will be appreciated that various of the above-disclosed and other features and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Also that various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompassed by the following claims.

While the above description is directed to particular embodiments, it will be appreciated that many changes can be made without departing from the spirit of the invention. The claims are intended to cover such modifications as would fall within the true scope and spirit of the embodiments herein.

The presently disclosed embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the embodiments being indicated by the appended claims, rather than the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Examples

The examples hereinafter set forth and illustrate various compositions and conditions that may be used in the practice of embodiments of the present invention. All proportions are by weight unless otherwise indicated. It is clear, however, that embodiments of the invention can be practiced with many types of compositions and can have many different uses in accordance with the disclosure above and as pointed out hereinafter.

Example 1

Preparation of oligoamide ester resin (resin 1 of Table 1)

The oligomeric amidoester resin of this example is a representative example of a resin, starting with 1, 12-dodecanedioic acid and 6-aminohexanol as monomers, and dodecanol (lauryl alcohol) as an end-capping agent, prepared as follows:

as shown above, 6-aminohexanol was reacted with 1, 12-dodecanedioic acid, with dodecanol or lauryl alcohol as the end-capping agent, to produce an oligomeric amide ester. To a 100mL three-necked round bottom flask equipped with an argon inlet, a temperature probe connected to a digital temperature controller, a magnetic stir bar, and a short path distillation head was added: 1.172g (10.0mmol) of 6-aminohexanol (mp 55 ℃ C.) and 3.455g (15mmol) of 1, 12-dodecanedioic acid (mp 128 ℃ C.), finally 1.863g (10mmol) of dodecanol (lauryl alcohol). The reaction mixture was heated to melt (. about.100 ℃) with stirring at 400 rpm. At this temperature, 4.2mg (0.002 equivalents; 20.1. mu. mol) of FASCAT4100 (n-BuSnO)₂H, ex Arkema) was added to the flask and the reaction mixture was gradually heated to 165 ℃ for 2 hours. At-135 c it was found that water vapour was released, at which temperature all reagents melted. After 2 hours, the temperature was raised to 180 ℃ and maintained for an additional 1 hour.

Conversion rate of reaction by¹H-NMR and¹³C-NMR analysis was followed at intervals of 30, 45, 60, 90, 120 and 180 minutes.¹H-NMR analysis showed that all 6-aminohexanol reacted in 180 minutes. Followed by application of high vacuum (<0.1mmHg) for about 5 minutes to remove excess H trapped in the molten resin₂And O is a byproduct. The molten resin was poured directly (neat) into a tared beaker to give an opaque beige resin in a yield of 4.4 g. Chemical structure of the productIs composed of¹The H-NMR spectrum confirmed.

The resin product was thermally analyzed by DSC over two successive heating and cooling cycles using a scan rate of 10 ℃/min, which analysis indicated that the resin material had both crystalline and amorphous characteristics, since the thermal profile exhibited three distinct melting point transitions at 48 ℃,64 ℃ and 90 ℃ (peaks), as well as a glass transition (Tg) at an initial temperature of 26 ℃.

The rheometry was carried out using a Rheometrics RFS3 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry tool, 200% strain) at a temperature range of 50 ℃ to 130 ℃. FIG. 1 shows a complex viscosity versus temperature graph showing that this material is semi-crystalline, undergoes a sharp crystalline phase transition at about 76 ℃ and has a melt viscosity of-50 cPs at 130 ℃.

Example 2

Preparation of oligoamide ester resin (resin 2 of Table 1)

The oligoamide ester resin of this example was prepared in a similar procedure and on the same scale as the resin of example 1, except that p-methoxybenzyl alcohol (1.38g,10.0mmol) was used as the capping agent in place of dodecanol. Conversion rate of reaction is controlled by¹H-NMR and¹³C-NMR was followed up to 3 hours, after which time,¹H-NMR analysis showed that all 6-aminohexanol had reacted. Applying a high vacuum (<0.1mmHg) for about 5 minutes to remove excess H trapped in the mixture₂O, and then the mixture was poured into a container to obtain an opaque beige resin in a yield of 5.23 g. The chemical structure of the product consists of¹The H-NMR spectrum confirmed. Rheological analysis was performed using a rheometrics rfs3 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry tool, 200% strain) at a temperature range of 50 ℃ to 130 ℃. FIG. 1 shows a complex viscosity versus temperature graph showing that this material is semi-crystalline, undergoes a sharp crystalline phase transition at about 75 ℃ and has a melt viscosity of-74 at 130 ℃.5cPs。

Example 3

Preparation of oligoamide ester resin (resin 3 of Table 1)

The oligomeric amidoester resin of this example is a representative example of a resin, starting with C36-dimer acid monomer, prepared as follows:

as described above, PRIPOL1006 (C-36 dimer diacid, available from CRODA Inc.) was reacted with 6-aminohexanol and UNILIN 350 (x-21 carbon units, available from Baker-Petrolite) as the end-capping agent to prepare the oligoamide ester. In embodiments, NMR confirms that the oligomeric amide ester resin structure has n ═ 2 and x to 21 carbon units.

A 100ml reaction kettle equipped with a stir bar, a four-neck stopper with a thermocouple connected to a digital temperature controller, an argon inlet, and a short path distillation head was charged with: 18.44g (32mmol) Pripol1006 (a C-36 dimer diacid available from CRODA Inc.), 2.52g (22mmol) 6-aminohexanol available from Sigma Aldrich, and 0.02g (0.096mmol) FASCAT4100(n-BuSnO₂H; available from Arkema). The reaction mixture was gradually heated to 180 ℃ with stirring and heating was continued for 4 hours, condensation being first observed at 130 ℃. The heating was stopped and the reaction mixture was cooled to 100 ℃ and 8.91g (24mmol) of Unilin 350 (a monocarboxylic acid from Baker Petrolite) was added. The reaction mixture was gradually heated to 180 ℃ with stirring and held at 180 ℃ for 3 hours, during which time more water was collected. The heating was stopped and the product was cooled to 120 ℃ and poured into tared aluminum pans to give 19.5g of a beige solid.¹H-NMR analysis confirmed that n-2 of the structure.

Example 4

Preparation of oligoamide ester resin (resin 4 of Table 1)

The oligomeric amidoester resin of this example was prepared in a similar procedure and on the same scale as the resin of example 1, except that hexadecane-1-ol was used as the end-capping agent instead of dodecanol. The chemical composition of the product consists of¹The H-NMR spectrum confirmed. Rheological analysis using a Rheometrics RFS3 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry tool, 200 strain%) at a temperature range of 50 ℃ to 130 ℃ indicated that this material was semi-crystalline, had a sharp crystalline phase transition at about 70 ℃, and had a melt viscosity of-26.5 cPs at 130 ℃.

Example 5

Preparation of oligoamide ester resin (resin 5 of Table 1)

The oligoamide ester resin of this example was prepared in a similar procedure and on the same scale as the resin of example 1, except that 1, 12-decanoic acid and 4- (methoxyphenyl) methanol were used as the capping agent instead of dodecanol. The chemical composition of the product consists of¹The H-NMR spectrum confirmed. Rheological analysis using a Rheometrics RFS3 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry tool, 200 strain%) at a temperature range of 50 ℃ to 130 ℃ indicated that this material was semi-crystalline, had a sharp crystalline phase transition at about 76 ℃, and had a melt viscosity of-50 cPs at 130 ℃.

Example 6

Preparation of oligoamide ester resin (resin 6 of Table 1)

The oligoamidoester resin of this example was prepared in a similar procedure and on the same scale as the resin of example 1, except that 10 mole% of 1, 4-cyclohexanedicarboxylic acid and 90 mole% of 1, 12-decanoic acid were used instead of 100 mole% of 1, 12-decanoic acid and hexadecane-1-ol was used instead of dodecanol as the end-cappingAnd (3) preparing. The chemical composition of the product consists of¹The H-NMR spectrum confirmed. Rheological analysis using a Rheometrics RFS3 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry tool, 200 strain%) at a temperature range of 50 ℃ to 130 ℃ indicated that this material was semi-crystalline, had a sharp crystalline phase transition at about 76 ℃, and had a melt viscosity of-50 cPs at 130 ℃.

Example 7

Preparation of oligoamide ester resin (resin 7 of Table 1)

The oligomeric amide ester of this example was prepared using reagents similar to those of example 1, with the following changes: the reaction mixture was gradually heated up to 160 ℃ for 1 hour. The temperature was raised to 180 ℃ and held at this temperature for 3 hours. The temperature is reduced to 160 ℃ and a high vacuum is applied (<0.1mmHg) for about 10 minutes to remove excess H trapped in the molten resin₂And O is a byproduct. The molten resin was poured directly into a tared beaker. The chemical structure of the product consists of¹The H-NMR spectrum confirmed.

The resin product was thermally analyzed by DSC over two successive heating and cooling cycles using a scan rate of 10 ℃/min, which analysis indicated that the resin material had both crystalline and amorphous characteristics, since the thermal profile exhibited three distinct melting point transitions at 44 ℃,59 ℃,78 ℃ and 91 ℃ (peaks), as well as a glass transition (Tg) at an initial temperature of 29 ℃.

Rheological analysis was performed at a temperature range of 50 ℃ to 140 ℃ using an Ares-G2 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry, 200% strain applied). The rheological curve shows that this material is semi-crystalline, undergoes a sharp crystalline phase transition at about 71 ℃, and has a melt viscosity of-31 cPs at 130 ℃.

Example 8

Preparation of oligoamide ester resin (resin 8 of Table 1)

The oligomeric amidoester resin of this example was prepared in a similar procedure and on the same scale as the resin of example 7, except that 2-phenylethyl alcohol was used as the end-capping agent instead of dodecanol. The chemical structure of the product consists of¹The H-NMR spectrum confirmed.

Rheological analysis was performed at a temperature range of 50 ℃ to 130 ℃ using an Ares-G2 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry, 200% strain applied). The rheological curve shows that this material is semi-crystalline, undergoes a sharp crystalline phase transition at about 73 ℃, and has a melt viscosity of-41 cPs at 130 ℃.

Example 9

Preparation of the phase-Change component (Compound 2 of Table 3)

C-11 alkylated mono-oxazoline diol is one representative example of a suitable phase change component of an oligomeric amide ester semi-crystalline ink, and is prepared as follows.

A1 liter Parr reactor equipped with a twin turbine agitator and distillation apparatus was charged with 200g of lauric acid, 92g of tris (hydroxymethyl) aminomethane (a.k.a.TRIS-AMINO), and 0.45g of stannic acid (stannoic acid) (Fascat 4100, available from Arkema Inc). The contents were heated to 165 ℃ and held for 2 hours, after which the temperature was raised to 205 ℃ over 2 hours, with the water collected in the distillation receiver. The pressure of the reactor was then reduced to about 1-2mm-Hg for 1 hour, after which the contents were poured into a metal dish. The product was then dissolved by heating in a mixture of ethyl acetate (2.5 parts) and hexane (10 parts) and allowed to cool to room temperature, whereby the pure product was obtained as a white crystalline powder after filtration. M.pt. (determined by DSC): 99 deg.C (peak).

Example 10

Preparation of the phase-Change component (Compound 1 of Table 3)

To a 200mL three-necked round bottom flask equipped with a reflux condenser and a constant pressure dropping funnel was added 1, 3-bis (isocyanatomethyl) cyclohexane (1.32g, 6.8 mmol; commercially available from Aldrich chemical Ltd., Milwaukee, USA), and anhydrous hexane (30mL) as a solvent. The mixture was mechanically stirred to give a homogeneous solution, called "solution A". In a separate vessel, stearyl alcohol (3.68g, 13.6 mmol; stearyl alcohol, available from Aldrich Chemical Ltd.) was dissolved in a 1:1 mixture of anhydrous hexane and anhydrous Tetrahydrofuran (THF) solvent until a clear solution (called "solution B") was obtained. Dibutyltin (IV) dilaurate (86mg) was added to the solution B as a catalyst, and the solution was transferred to a dropping funnel. Solution B was added slowly to solution a with stirring at room temperature. At the end of the addition, the entire mixture in the round-bottom flask was gradually heated to an internal temperature of about 50 ℃ and kept at this temperature for about 90 minutes. After this time, the reaction is complete (from¹H-NMR monitoring confirmed) and a product precipitate was observed in the form of a suspension in the solvent mixture. About 10ml of methanol was added to the mixture to ensure quenching of the residual isocyanate reagent. The solvent was removed in vacuo and the precipitate was filtered and washed with cold hexane to give 4.78g (97.5% yield) of the product as a pure white powder. For composition of products¹H-NMR spectrum and elemental analysis (C, H, N).

Example 11

Preparation of oligoester resin (resin 1 of Table 2)

The oligoester resin of this example was prepared as follows:

the oligomeric esters are prepared by reacting hexane-1, 6-diol with 1, 12-dodecanedioic acid, as indicated above, using dodecanol or lauryl alcohol as the end-capping agent. Is provided withA 100mL three-necked round bottom flask with an argon inlet, a temperature probe connected to a digital temperature controller, a magnetic stir bar, and a short path distillation head was charged with: 3.55g (30.0mmol) of hexane-1, 6-diol and 10.36g (45mmol) of 1, 12-dodecanedioic acid, and finally 5.59g (30mmol) of dodecanol (lauryl alcohol). The reaction mixture was heated with stirring at 400rpm until molten (-100 ℃). At this temperature, 0.013mg (0.06mmol) of FASCAT4100 (n-BuSnO)₂H, ex Arkema) was added to the flask and the reaction mixture was gradually heated up to 160 ℃ for 1 hour. Evolution of water vapor was observed at-135 ℃, at which temperature all reagents melted. After 1 hour, the temperature was raised to 185 ℃ and heated for an additional 3.5 hours.

The molten resin was cooled to 160 ℃ and poured directly into a tared beaker to give 14.5g of an opaque beige resin. The chemical structure of the product consists of¹The H-NMR spectrum confirmed.

Rheological analysis was performed at a temperature range of 50 ℃ to 140 ℃ using an Ares-G2 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry, 200% strain applied). The rheological curve shows that this material is semi-crystalline, undergoes a sharp crystalline phase transition at about 51 ℃ and has a melt viscosity of 11.3cPs at 140 ℃.

Example 12

Preparation of oligoester resin (resin 2 of Table 2)

Hexane-1, 6-diol was reacted with 1, 12-dodecanedioic acid as follows:

a 100mL three-necked round bottom flask equipped with an argon inlet, a temperature probe connected to a digital temperature controller, a magnetic stir bar, and a short path distillation head was charged with: 4.0g (33.8mmol) of hexane-1, 6-diol and 15.59g (67.7mmol) of 1,12Dodecanedioic acid. The reaction mixture was heated with stirring at 400rpm until molten (-140 ℃). At this temperature, 0.014mg (0.068mmol) of FASCAT4100 (n-BuSnO)₂H, ex Arkema) was added to the flask and the reaction mixture was gradually heated up to 160 ℃ for 1 hour. After 1 hour, the temperature was raised to 185 ℃ and held for an additional 4.5 hours.

The molten resin was cooled to 160 ℃ and poured directly into a tared beaker to give 16.9g of an opaque beige resin. The chemical structure of the product consists of¹The H-NMR spectrum confirmed.

The resin product was thermally analyzed by DSC over two successive heating and cooling cycles using a scan rate of 10 ℃/min, which analysis indicated that the resin material had both crystalline and amorphous characteristics, since the thermal profile exhibited three distinct melting point transitions at 78 ℃ and 106 ℃ (peaks), as well as a glass transition (Tg) at an initial temperature of 42 ℃.

Rheological analysis was performed at a temperature range of 50 ℃ to 140 ℃ using an Ares-G2 instrument (oscillation frequency 1Hz, 25mm parallel plate geometry, 200% stress applied). The rheological curve shows that this material is semi-crystalline, undergoes a sharp crystalline phase transition at about 83 ℃, and has a melt viscosity of-16.5 cPs at 140 ℃.

Example 13

Preparation of solid ink composition (ink example 1 of Table 4)

As a representative example, a solid ink comprising a semi-crystalline oligomeric amide ester resin (resins of examples 1 and 2 of Table 1) and a crystalline phase change component (example 2 of Table 3, phase change component) was prepared in the following manner.

The following components were added in the following order to a 60ml brown glass beaker: 1) oligomeric amide ester resin of example 1 resin (1.61g, or 16% by weight of ink); 2) oligoamide ester resin of example 2 (1.23g, or 12.3% by weight of ink); recrystallized C11-alkylated monooxazoline diol of example 2 of table 3 (6.40g, or 64.0% by weight of the ink); 3) viscosity modifier S-180(0.44g, or 4.4% by weight of the ink; available as Kemamide or stearyl stearamide); 4) orasol Blue GN dye (0.3g, or 3% by weight of ink, available from Ciba Geigy); and 5) Naugard 445 antioxidant (0.02g, or 0.2% by weight of the ink). The ink components were melted at 130 ℃ while magnetically stirring at 350rpm for at least 1 hour, after which time they were poured into a mold and cooled to a solid ink.

The ink had a uniform blue appearance throughout the sample and a viscosity of 12.5cPs at 130 ℃ as measured by an RFS3 strain controlled rheometer (constant frequency 1 Hz; using a 25mm parallel plate geometry tool) and had an initial crystallization temperature (as measured by rheology) of 82 ℃ and a narrow liquid-to-solid phase transition spanning 85 to 75 ℃ (about 10 ℃ range).

Example 14

Preparation of solid ink composition (ink example 2 of Table 4)

Preparation of ink in example 13 solid inks comprising a semi-crystalline oligoamide ester resin and a crystalline phase change component as given in table 4 were prepared according to the same method as in example 1.

Example 15

Preparation of solid ink composition (ink example 3 of Table 4)

Example 16

Preparation of solid ink composition (ink example 4 of Table 4)

Preparation of ink in example 13 solid inks comprising a semi-crystalline oligoamide ester resin and a viscosity modifier as given in table 4 were prepared according to the same method as in example 1.

Example 17

Preparation of solid ink composition (ink example 5 of Table 4)

The claims, as originally presented and as they may be amended, encompass variations, alternatives, modifications, improvements, equivalents, and substantial equivalents of the embodiments and teachings disclosed herein, including those that are presently unforeseen or unanticipated and that, for example, may arise from applicants/patentees and others. Unless specifically recited in a claim, the steps or components of a claim should not be inferred or inferred from the description or any other claims as to any particular order, number, position, size, shape, angle, color, or material.

All patents and patent applications mentioned herein are hereby specifically and fully incorporated by reference in their entirety into this specification.

Claims

1. A solid phase change ink comprising:

a semi-crystalline oligomeric resin selected from the group consisting of oligomeric esters and oligomeric amide esters;

optionally a colorant; and

an ink vehicle wherein the semi-crystalline oligomeric resin is prepared from the condensation reaction of a dicarboxylic acid or anhydride or diester, a difunctional alkanol monomer, and optionally a monofunctional capping reactant,

wherein,

the oligomeric ester has the formula:

wherein R is₁、R₂And R₃Independently of one another, is substituted or unsubstituted, with or without heteroatoms, and wherein R is₁Is an alkylene group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; arylene having 6 to 20 carbon atoms; or an aralkylene group having 7 to 20 carbon atoms; r₂Is an alkylene group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; arylene having 6 to 20 carbon atoms; or an aralkylene group having 7 to 20 carbon atoms; r₃Is H; an alkyl group having 1 to 50 carbon atoms; an aryl group having 6 to 50 carbon atoms; or an alkaryl group having from 7 to 50 carbon atoms; and n is a number from 1 to 10,

the oligomeric amide ester has the formula:

wherein R is₁、R₂And R₃Independently of one another, is substituted or unsubstituted, with or without heteroatoms, and wherein R is₁Is an alkylene group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; arylene having 6 to 20 carbon atoms; or an aralkylene group having 7 to 20 carbon atoms; r₂Is an alkylene group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; arylene having 6 to 20 carbon atoms; or an aralkylene group having 7 to 20 carbon atoms; r₃Is H; an alkyl group having 1 to 50 carbon atoms; an aryl group having 6 to 50 carbon atoms; or an alkaryl group having from 7 to 50 carbon atoms; and n is a number from 1 to 10.

2. The solid phase change ink of claim 1 wherein the oligoester resin is prepared by polycondensation of a monomer consisting of two or more reactive functional groups, optionally a monofunctional capping reactant, selected from the group consisting of linear, branched and cyclic alkane dicarboxylic acids, ethylenically unsaturated dicarboxylic acids, arene dicarboxylic acids, alkyl arene dicarboxylic acids, aryl alkane dicarboxylic acids, hydroxy-substituted carboxylic acids, polyols; the capping reactant is selected from the group consisting of straight, branched and cyclic alkanols, ethylenically unsaturated alkanols, aryl alkanols, and mixtures thereof.

3. The solid phase change ink of claim 2 wherein the polyol is selected from the group consisting of alkane diols, ethylenically unsaturated diols, hydroxyl substituted diols, alkyl aromatic diols, aryl alkane diols.

4. The solid phase change ink of claim 2 wherein the cyclic alkane dicarboxylic acid is a polycycloalkane dicarboxylic acid and the hydroxy-substituted carboxylic acid is a hydroxy-substituted dicarboxylic acid.

5. The solid phase change ink of claim 1 wherein the oligomeric amide ester resin is prepared from monomers consisting of two or more reactive functional groups, optionally a monofunctional capping reactant, said monomers selected from the group consisting of linear, branched and cyclic alkane dicarboxylic acids, ethylenically unsaturated dicarboxylic acids, arene dicarboxylic acids, alkyl arene dicarboxylic acids, aryl alkane dicarboxylic acids, primary-and secondary-aminoalkanols, hydroxy substituted aminoalkanols, ethylenically unsaturated aminoalkanols, aminocarboxylate esters, hydroxy substituted alkaryl amines, hydroxy substituted aralkyl amines, polyhydroxy amines; the capping reactant is selected from the group consisting of straight, branched and cyclic alkanols, ethylenically unsaturated alkanols, aryl alkanols, and mixtures thereof.

6. The solid phase change ink of claim 5 wherein the cyclic alkane dicarboxylic acid is a polycycloalkane dicarboxylic acid.

7. The solid phase change ink of claim 1 wherein the ink vehicle comprises a crystalline compound.

8. The solid phase change ink of claim 7 wherein the crystallization temperature of the ink vehicle is within ± 15 ℃ of the crystallization temperature of the oligomeric resin.

9. The solid phase change ink of claim 1 wherein the ink has a melting temperature of 80 ℃ or greater.

10. The solid phase change ink of claim 9 wherein the ink has a melting temperature of 80 to 130 ℃.

11. The solid phase change ink of claim 1 wherein the ink has a crystallization temperature of from 50 to 110 ℃.

12. The solid phase change ink of claim 11 wherein the ink has a crystallization temperature of from 60 to 100 ℃.

13. The solid phase change ink of claim 1 wherein the viscosity of the ink is greater than 1 × 10 over a temperature range of 20 ℃ to 60 ℃⁶cPs。

14. The solid phase change ink of claim 1 wherein the ink vehicle further comprises other crystalline components present in an amount of 1 to 70% by weight of the ink.

15. The solid phase change ink of claim 1 having a phase transition from a liquid, i.e., molten, state to a solid, i.e., crystalline, state at a temperature of from 50 ℃ to 110 ℃.

16. The solid phase change ink of claim 1 having an ink crystal phase transition from liquid to solid in the temperature range of 5 ℃ to 15 ℃.

17. The solid phase change ink of claim 1, wherein the semi-crystalline oligomer resin has a molecular weight of 500 to 2,500 g/mol.

18. A solid phase change ink comprising:

a colorant; and

wherein X is O, NH, and mixtures thereof, and in the presence of an optional end-capping agent R₃The group Z ═ O or NH in ZH, and R₁、R₂And R₃Independently of one another, is substituted or unsubstituted, with or without heteroatoms, and wherein R is₁Is an alkylene group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; arylene having 6 to 20 carbon atoms; or an aralkylene group having 7 to 20 carbon atoms; r₂Is an alkylene group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; arylene having 6 to 20 carbon atoms; or an aralkylene group having 7 to 20 carbon atoms; r₃Is H; an alkyl group having 1 to 50 carbon atoms; an aryl group having 6 to 50 carbon atoms; or an alkaryl group having from 7 to 50 carbon atoms; and n is a number from 1 to 10,

and wherein the one or more of the one,

the oligomeric ester has the formula:

wherein R is₁、R₂And R₃Independently of one another, substituted or unsubstituted, with or without the presence ofAt a heteroatom, and, wherein R₁Is an alkylene group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; arylene having 6 to 20 carbon atoms; or an aralkylene group having 7 to 20 carbon atoms; r₂Is an alkylene group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; arylene having 6 to 20 carbon atoms; or an aralkylene group having 7 to 20 carbon atoms; r₃Is H; an alkyl group having 1 to 50 carbon atoms; an aryl group having 6 to 50 carbon atoms; or an alkaryl group having from 7 to 50 carbon atoms; and n is a number from 1 to 10,

the oligomeric amide ester has the formula:

19. The solid phase change ink of claim 18 wherein the ratio of dicarboxylic acid to difunctional alkanol monomer is from 2:1 to 0.5: 1.

20. A solid phase change ink comprising:

a semi-crystalline oligomeric amide or ester resin;

a colorant; and

an ink vehicle wherein the oligomeric amide ester resin has the formula:

wherein R is₁、R₂And R₃Independently of one another, and is substituted or unsubstituted, and wherein R₁Is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an alkyleneoxy group having 1 to 20 carbon atoms; or an aryl or heteroaryl group having 4 to 10 carbon atoms; r₂Is a linear, branched or cyclic alkyl group having 1 to 50 carbon atoms; an aryl group having 1 to 14 carbon atoms; an alkaryl group having from 1 to 25 carbon atoms; or an ethylenically unsaturated alkyl group having 1 to 50 carbon atoms; r₃Is H; a linear, branched, ethylenically unsaturated, or cyclic alkyl group having 1 to 50 carbon atoms; an aryl or alkaryl group having from 1 to 25 carbon atoms; or an alkyleneoxy group having 1 to 20 carbon atoms; and n is a number from 1 to 10, and the oligoester resin has the formula:

wherein R is₁、R₂And R₃Independently of one another, and is substituted or unsubstituted, and wherein R₁Is a linear, branched or cyclic alkyl group having 1 to 50 carbon atoms; an ethylenically unsaturated alkyl group having 1 to 40 carbon atoms; or an alkylaryl group having from 1 to 20 carbon atoms; r₂Is a linear, branched or cyclic alkyl group having 1 to 50 carbon atoms; an aryl group having 1 to 14 carbon atoms; an alkaryl group having from 1 to 25 carbon atoms; or an ethylenically unsaturated alkyl group having 1 to 50 carbon atoms; r₃Is H; a linear, branched, ethylenically unsaturated, or cyclic alkyl group having 1 to 50 carbon atoms; an aryl or alkaryl group having from 1 to 25 carbon atoms; or an alkyleneoxy group having 1 to 20 carbon atoms.

21. The solid phase change ink of claim 20 wherein the oligomeric polyesteramide or oligoester resin is present in an amount of 10 to 90 weight percent based on the total weight of the solid phase change ink.